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WO2010094988A1 - Procédé de production d'un aérogel lithium-métal (ii) phosphate amorphe par une méthode sol-gel non aqueuse - Google Patents

Procédé de production d'un aérogel lithium-métal (ii) phosphate amorphe par une méthode sol-gel non aqueuse Download PDF

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Publication number
WO2010094988A1
WO2010094988A1 PCT/IB2009/000307 IB2009000307W WO2010094988A1 WO 2010094988 A1 WO2010094988 A1 WO 2010094988A1 IB 2009000307 W IB2009000307 W IB 2009000307W WO 2010094988 A1 WO2010094988 A1 WO 2010094988A1
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WIPO (PCT)
Prior art keywords
aerogel
phosphate
lithium metal
previous
amorphous
Prior art date
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Ceased
Application number
PCT/IB2009/000307
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English (en)
Inventor
Jun Yoshida
Norio Sato
Nicola Huesing
Michael Stark
Jürgen HOLZBOCK
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Toyota Motor Corp
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Toyota Motor Corp
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Priority to PCT/IB2009/000307 priority Critical patent/WO2010094988A1/fr
Publication of WO2010094988A1 publication Critical patent/WO2010094988A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J13/00—Colloid chemistry, e.g. the production of colloidal materials or their solutions, not otherwise provided for; Making microcapsules or microballoons
    • B01J13/0091—Preparation of aerogels, e.g. xerogels

Definitions

  • the invention relates to a method of producing an amorphous lithium metal (II) phosphate aerogel and an amorphous lithium metal (II) phosphate aerogel, wherein the porosity of the aerogel is higher than 80%.
  • Batteries belong to the most important power sources which are used in different areas of operation. Almost any electrical consumer can be equipped with batteries in order to use electrical energy which results from discharging of the battery through an electrochemical redox reaction.
  • Lithium is a widespread negative electrode material for batteries. This Is due to the fact that lithium has the most negative standard potential of all elements which allows realizing obtaining high battery cell voltages. Also, using lithium theoretically extremely high battery capacities are accomplishable. Indeed, since many years suitable electrode materials are developed for uptaking and releasing of lithium ions in combination with respective electrolyte materials in order to achieve such high theoretical energy densities of lithium batteries in practice.
  • One electrode material which can be used to realize such high discharge voltages while maintaining a high capacity are lithium phosphor compounds in the form of olivines, as for example LiMPO 4 , wherein M is a metal like iron, manganese, cobalt etc.
  • LiMPO 4 transition metal
  • M transition metal
  • Immense technical efforts have therefore been devoted to counteract this problem, one approach being the synthesis of well dispersed and small particles to shorten the diffusion path length of lithium ions.
  • phospho-olivine is a positive electrode material suitable for rechargeable lithium batteries.
  • J. Electrochem. Soc, Vol. 148, No. 8, A960 ⁇ A967, 2001 deals with the usage of olivine type lithium compounds as a possible cathode material for lithium batteries.
  • US 5,910,382 discloses the usage of transition metal compounds with an ordered olivine or rhombohedral Nasicon structure as electrode material for rechargeable alkali ion batteries.
  • porous LiMPO 4 /C composites where M stands for Fe and/or Mn
  • the document discusses porosity in terms of qualitative results obtained from TEM micrographs and in terms of quantitative results obtained from N 2 adsorption. Porous particles are described as an inverse picture of nano particulate arrangements, where the pores serve as channels for lithium supply and the distance between the pores determines the material kinetics.
  • Optimized, well crystallized phosphates have also been synthesized by a sol-gel approach also termed as "chimielactic reaction 11 and low sintering temperatures as disclosed in WO2007/093856. Drying of the resulting gel body is performed at low temperatures in ambient pressures, resulting in a material that the authors describe as an aerogel. This aerogel is converted to crystalline LiMnPO 4 by sintering in a second step. No further evidence on the aerogel structure is given in the disclosure. Aerogels are highly porous solid materials with extremely low densities (bulk densi- ties 0.004 - 0.500 g/cm 3 ), large, open pores, and high specific surface areas. So far, aerogels have been differently defined: 1.
  • Aerogels All materials prepared from wet gels by supercritical drying were called aerogels, irrespective of their structural properties. However, with the development of new drying techniques this definition is no longer appropriate or 2.
  • Materials in which the typical pore structure and network are largely maintained when the pore liquid of a gel is replaced by air are called aerogels. Typically drying by simply heating a highly porous gel does not result In an aerogel. [Aerogels, N. H ⁇ sing, U. Schubert, Uflmann's Encyclopedia of Industrial Chemistry, Sixth Edition, 2000 Electronic Release, Wiley VCH, Weinheim 2006].
  • US, 4,622,310 discloses the preparation of inorganic phosphate aerogels and the method of preparing such inorganic phosphate aerogels which are characterized by high surface areas and high pore volumes.
  • the present invention provides a method of producing an amorphous lithium metal (II) phosphate aerogel, the method comprising dissolving a lithium salt and a metal salt in a first organic solvent, dissolving a phosphor source in the first organic solvent, mixing the dissolved salts and the dissolved phosphor source to receive a monolithic gel and supercritical drying of the gel for receipt of the lithium metal (II) phosphate aerogel.
  • the method according to the invention has the advantage, that amorphous lithium metal (II) phosphates can be produced with an extremely high surface area.
  • the morphology of the lithium metal (II) phosphate amorphous nanoparticles forming a threedimensional network can further be easily controlled.
  • the preparation of such kind of lithium metal (II) phosphate material which is built- up from amorphous nanoparticles forming a nanoporous network with a high surface area is an important step for production of highly efficient cathode materials for lithium ion batteries.
  • lithium metal (II) phosphate material By coating the lithium metal (II) phosphate material with carbon and starting a crystallization process, carbon coated crystal lithium metal (II) phosphate nanoparticles can be obtained which have a high electronic and ionic conductivity which permits the application of the resulting material as negative electrode material in batteries with extremely high charge and discharge rates.
  • amorphous lithium metal (II) phosphate aerogel By means of the method of producing an amorphous lithium metal (II) phosphate aerogel, a material can be obtained which allows for high performance applications in lithium ion batteries.
  • the method further comprises adding acetic acid to the dissolved salts.
  • Acetic acid acts as a compatibilizing agent, is needed for pH-adjustment and can act as chelating species to control the chemical reactivity of the salts.
  • carboxylic acids are also suited.
  • the method further comprises adding hydrazine hydrate to the dissolved salts.
  • Hydrazine hydrate acts as a reducing agent to avoid oxidation of Mn(II) to Mn(III) or other species.
  • the method further comprises exchanging the first organic solvent with a second organic solvent.
  • Exchanging the first organic solvent with a second organic solvent has the advantage, that during the supercritical drying process of the gel an unwanted partial drying of the wet gel can be efficiently avoided. This is an important aspect in order to prevent shrinkage of the gel volume before or during supercritical drying.
  • the supercritical drying Is performed in the presence of the second organic solvent.
  • the first solvent comprises DMSO.
  • the second solvent comprises methanol.
  • DMSO lithium and metal salts can be easily dissolved in the solvent.
  • the combination of DMSO and methanol has the advantage, that a highly efficient solvent exchange within a short period of time is achievable which is an important aspect for industrial scale processes where processing speed is an important aspect.
  • the lithium salt comprises lithium acetate.
  • the phosphor source comprises a phosphate and/or a phosphoric acid component.
  • the invention in another aspect, relates to a method of producing a battery electrode material, wherein the method comprises the method of producing an amorphous lithium metal (II) phosphate aerogel according to the invention, the method further comprising mixing the aerogel with the carbon source for receipt of amorphous carbon coated nanoparticles and subsequent heat treating of said nanoparticles for formation of carbon coated crystalline lithium metal (II) phosphate nanoparticles.
  • the method comprises the method of producing an amorphous lithium metal (II) phosphate aerogel according to the invention, the method further comprising mixing the aerogel with the carbon source for receipt of amorphous carbon coated nanoparticles and subsequent heat treating of said nanoparticles for formation of carbon coated crystalline lithium metal (II) phosphate nanoparticles.
  • such kinds of carbon coated crystalline lithium metal (II) phosphate nanoparticles have the advantage, that due to the nanometer sized dimensions of the particles highly efficient lithium ion batteries can be realized by using said carbon coated crystalline lithium metal (II) phosphate nanoparticles as negative battery electrode material.
  • the mixing is performed by milling, preferably ball milling.
  • the carbon source comprises graphite and/or carbon black and/or acetylene black.
  • the invention relates to an amorphous lithium metal (II) phosphate aerogel, wherein the porosity of the aerogel is higher than 80%.
  • the lithium metal (II) phosphate aerogel is a monolithic aerogel.
  • Figure 1 is a flow chart illustrating a method of producing an amorphous lithium metal (II) phosphate aerogel and a battery electrode material
  • Figure 2 shows XRD measurement results performed on a heat treated and crystallized LiMnPO 4 aerogel
  • FIG. 3 shows XRD results of various in-situ heat treated LiMnPO 4 aerogels at different heating temperatures
  • Figure 4 shows the nitrogen sorption data for an amorphous LiMnPO 4 aerogel.
  • Figure 5 shows a TEM image of an amorphous LiMnPO 4 aerogel.
  • Fig. 1 is a flow chart illustrating the method of producing an amorphous lithium metal (II) phosphate aerogel and a battery electrode material according to the invention.
  • the method starts in step 100 in which a lithium salt and a metal salt are dissolved in a first organic solvent.
  • a lithium salt and a metal salt are dissolved in a first organic solvent.
  • manganese acetate and lithium acetate are dissolved in DMSO.
  • a few drops of acetic acid and of hydrazine hydrate are added with steering which reduces Mn(III) and results in an almost colorless solution.
  • step 102 o-phosphoric acid is dissolved in DMSO and added to the salts dissolved in step 100. This results in the formation of a gel.
  • step 104 this gel is 'aged' at elevated temperatures which may result in a small shrinkage of the monolithic gel body. After a short curing time at elevated temperature in which DMSO is removed from the gel to some extent, DMSO is exchanged to methanol for various hours.
  • step 106 which comprises supercritical drying of the gel.
  • This can be for example performed by means of an autoclave which for this purpose is preferably filled with methanol to avoid a partial drying of the gel body.
  • the autoclave is kept preferably at room temperature.
  • the monolithic gel body is placed in the autoclave in the extraction thimble to avoid fragmenting of the sample.
  • the specimen boat is loaded into the pressure chamber, the door of the autoclave is closed and then the fill valve on the pressure vessel is carefully opened.
  • the autoclave is filled with liquid CO 2 and the pressure increases.
  • This is followed by a substitution of the methanol mother liquid with liquid carbon dioxide.
  • This flushing process is performed until the solvents are completely exchanged.
  • the actual supercritical drying process is performed.
  • the gel is very sensitive towards compression.
  • the surface area measured by BET analysis is higher than 400 m 2 per gram
  • Steps 108 and 110 are only necessary if the aerogel resulting from the supercritical drying step 106 shall be used as a battery electrode material.
  • the aerogel is mixed for example by ball milling with a carbon source for receipt of amorphous carbon coated nanoparticles.
  • a crystallization process in step 110 is performed by heat treatment of the carbon coated amorphous particles.
  • the resulting carbon coated crystals have a stoichiometric composition of LiMnPO 4 .
  • the carbon coated crystals are nanoparticles which compared to conventional LiMnPO 4 preparation techniques have an extremely small diameter. The particle size is typically much less than 10nm.
  • the carbon coating has here two advantages: first, due to the carbon coating of the LiMnPO 4 nanoparticles, the material is made electrically conductive which is an important aspect for application as electrode material in lithium ion batteries. Second, due to the carbon coating during the heat treatment process for the formation of the crystalline LiMnPO 4 particles, no sintering between LiMnPO 4 particles occurs. In other words, the particles will not form larger crystallites during the heat treatment process such that extremely regular, nanometer sized LiMnPO 4 particles can be obtained.
  • Fig. 2 shows an XRD (X-ray diffraction) pattern of a heat treated LJMnPO 4 aerogel. It can be seen, that all visible peaks in the diffraction diagram can be identified belonging to pure LiMnPO 4 . Obviously, no impurities are present. In other words, the produced aerogel consists of pure LiMnPO 4 .
  • the measurements in fig. 2 were performed after heat treatment at 450 ° C which results in a crystalline, shrunken sample.
  • fig. 3 various in-situ temperature dependent XRD measurements on an aerogel which was produced according to the method illustrated in fig. 1 are shown. It can be seen, that at low temperatures almost no diffraction peaks are visible which is an indication for an amorphous aerogel. By gradually increasing the temperature, it can be seen that crystallization sets in above 300 0 C. Above 600 0 C, LiMnPO 4 seems to decompose into different crystalline phases.
  • Fig. 4 shows the gas ad- and desorption isotherms for an aerogel measured with nitrogen at 77K according to this invention.
  • the adsorbed volume of the gas (N 2 ) is depicted versus the relative pressure p/p°.
  • the adsorptive (N 2 ) is automatically and continuously admitted to the aerogel sample, thus providing a measure (volumetric determination) of the adsorption under quasi-equilibrium conditions.
  • the porous nature of the material is clearly seen and the sorption is characterized by a Type IV isotherm with a H1 hysteresis indicating mesoporosity.
  • the specific surface area was evaluated by applying the Brunauer-Emmett-Teller theory in a pressure range from 0.05-0.5 p/p° via a 5-point analysis. It is very high with above 400 m 2 g '1 and the total pore volume (at the highest value for p/p° close to 1) already indicates the high porosity of the sample.
  • the rather low bulk density of the monolith with 0.143 gem "3 confirms the high porosity of above 90% (the crystal density would be 3.34 gem '3 .
  • Fig. 5 is a TEM (transmission electron microscopy) image of an aerogel according to the invention.
  • the TEM analysis shows a rather featureless image which clearly indicates that the aerogel sample is amorphous. No particles larger than 10nm are found and the porous nature of the structure is visible.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Dispersion Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Battery Electrode And Active Subsutance (AREA)

Abstract

L'invention concerne un procédé de production d'un aérogel lithium-métal (II) phosphate amorphe, ce procédé consistant à dissoudre (100) un sel de lithium et un sel métallique dans un premier solvant organique; dissoudre une source de phosphore dans le premier solvant organique; mélanger (102) les sels dissous et la source de phosphore dissoute pour obtenir un gel; effectuer un séchage supercritique (106) du gel pour obtenir l'aérogel lithium-métal (II) phosphate.
PCT/IB2009/000307 2009-02-20 2009-02-20 Procédé de production d'un aérogel lithium-métal (ii) phosphate amorphe par une méthode sol-gel non aqueuse Ceased WO2010094988A1 (fr)

Priority Applications (1)

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PCT/IB2009/000307 WO2010094988A1 (fr) 2009-02-20 2009-02-20 Procédé de production d'un aérogel lithium-métal (ii) phosphate amorphe par une méthode sol-gel non aqueuse

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PCT/IB2009/000307 WO2010094988A1 (fr) 2009-02-20 2009-02-20 Procédé de production d'un aérogel lithium-métal (ii) phosphate amorphe par une méthode sol-gel non aqueuse

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622310A (en) * 1984-12-24 1986-11-11 Stauffer Chemical Company Inorganic phosphate aerogels and their preparation
WO2005058472A2 (fr) * 2003-12-19 2005-06-30 Scf Technologies A/S Systemes permettant de preparer des particules fines et d'autres substances
EP1798802A1 (fr) * 2004-08-30 2007-06-20 Nihon University Matériau conducteur de type lithium-ion utilisant un organogel de cellulose bactérienne, accumulateur lithium-ion incluant ce matériau et aérogel de cellulose bactérienne
US20070272902A1 (en) * 2006-05-25 2007-11-29 Aspen Aerogels, Inc. Aerogel compositions with enhanced performance
WO2008109611A1 (fr) * 2007-03-05 2008-09-12 Northwestern University Technology Transfer Program Aérogels semi-conducteurs issus d'agrégats chalcogénures présentant un large champ d'application

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4622310A (en) * 1984-12-24 1986-11-11 Stauffer Chemical Company Inorganic phosphate aerogels and their preparation
WO2005058472A2 (fr) * 2003-12-19 2005-06-30 Scf Technologies A/S Systemes permettant de preparer des particules fines et d'autres substances
EP1798802A1 (fr) * 2004-08-30 2007-06-20 Nihon University Matériau conducteur de type lithium-ion utilisant un organogel de cellulose bactérienne, accumulateur lithium-ion incluant ce matériau et aérogel de cellulose bactérienne
US20070272902A1 (en) * 2006-05-25 2007-11-29 Aspen Aerogels, Inc. Aerogel compositions with enhanced performance
WO2008109611A1 (fr) * 2007-03-05 2008-09-12 Northwestern University Technology Transfer Program Aérogels semi-conducteurs issus d'agrégats chalcogénures présentant un large champ d'application

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
FU L J ET AL: "Electrode materials for lithium secondary batteries prepared by sol-gel methods", PROGRESS IN MATERIALS SCIENCE, PERGAMON PRESS, GB, vol. 50, no. 7, 1 September 2005 (2005-09-01), pages 881 - 928, XP004941883, ISSN: 0079-6425 *
ISHINO M ET AL: "Mass production of hydrophobic silica aerogel and readout optics of Cherenkov light", NUCLEAR INSTRUMENTS & METHODS IN PHYSICS RESEARCH, SECTION - A:ACCELERATORS, SPECTROMETERS, DETECTORS AND ASSOCIATED EQUIPMENT, ELSEVIER, AMSTERDAM, NL, vol. 457, no. 3, 21 January 2001 (2001-01-21), pages 581 - 587, XP004314569, ISSN: 0168-9002 *
NICOLA HUESING, E.A.: "Periodically Mesostructured Silica Monoliths from Diol-Modified Silanes", CHEM. MATER., vol. 15, no. 14, 20 June 2003 (2003-06-20), pages 2690 - 2692, XP002554477 *
SATOSHI YODA ET AL: "Preparation of SiO2-TiO2 Aerogels Using Supercritical Impregnation", JOURNAL OF SOL-GEL SCIENCE AND TECHNOLOGY, KLUWER ACADEMIC PUBLISHERS, BO, vol. 19, no. 1-3, 1 December 2000 (2000-12-01), pages 719 - 723, XP019212738, ISSN: 1573-4846 *

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